CN103035879B - Positive pole piece for lithium-sulfur batteries and preparation method thereof - Google Patents
Positive pole piece for lithium-sulfur batteries and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a positive pole piece for lithium-sulfur batteries and a preparation method thereof. The preparation method comprises the following steps: evenly mixing a surface-modified sulfenyl composite active material, a conducting agent and a binding agent, coating the mixture on a current collector, drying twice, and pressing to obtain the positive pole piece. The surface-modified sulfenyl composite active material is prepared by coating nickel, copper or any other excellent-conductivity metal on uniform-granularity simple substance sulfur by chemical plating, wherein the granularity of the simple substance sulfur is 10 nm-10 mu m, the conducting metal for chemical plating is 0.1-10 nm thick, and the content of the conducting metal is 0.8-10 wt%. The temperature and time for the first drying are respectively 40-80 DEG C and 6-12 hours, and the temperature and time for the second drying are 100-120 DEG C and 3-8 hours. The first discharge specific capacity of the lithium-sulfur battery assembled from the positive pole piece and metal lithium is 843.8 mAh/g positive pole piece substance at room temperature under the 0.1C-time charging/discharging conditions, and the capacity attenuation after 100 cycles is lower than the second discharge specific capacity by 8%. In addition, the invention has the advantages of simple preparation technique and low cost, and is beneficial to industrial production.
Description
Technical field
The present invention relates to lithium-sulfur cell field, especially relate to anode pole piece of a kind of lithium-sulfur cell and preparation method thereof.
Background technology
Along with the develop rapidly of portable electric appts, electric tool and space technology, the energy density of secondary cell is had higher requirement, but, traditional lithium rechargeable battery is due to the restriction by the theoretical lithium storage content of positive electrode, be difficult to make a breakthrough, as LiCoO in lifting energy density
2, LiNiO
2, LiMn
2o
4and LiFePO
4theoretical specific capacity be respectively 275mAh/g, 274mAh/g, 148mAh/g and 170mAh/g, therefore, find new battery system, develop new positive and negative pole material and seem particularly important.In new energy storage system, the theoretical specific energy of lithium-sulfur cell (elemental sulfur be positive pole, lithium metal be negative pole) is 2600Wh/kg, far away higher than current business-like secondary cell system, wherein the theoretical specific capacity of elemental sulfur and lithium is respectively 1675mAh/g and 3860mAh/g, in addition, elemental sulfur also has rich reserves, environmental friendliness, the advantage such as cheap, so lithium-sulfur secondary battery system enjoys the concern of people.
Lithium-sulfur cell elemental sulfur room temperature utilization efficiency is low, cycle performance is poor is subject matter of its application of restriction, the electron conduction of elemental sulfur and all very low (room-temperature conductivity 5 × 10 of ionic conductivity under room temperature
-30s/cm), cause the electro-chemical activity of sulphur in electrode poor, the problems such as utilance is low, meanwhile, the polysulfide ion produced in lithium-sulfur cell discharge process is soluble in electrolyte, reduces the utilance of active sulfur, produce " effect of shuttling back and forth " simultaneously, cause the corrosion of negative pole and the internal resistance of cell to increase, cause cycle performance to be deteriorated, capacity is decayed gradually.Therefore, strengthen the electric conductivity of elemental sulfur, promote its electro-chemical activity, reduce the dissolving of polysulfide, be promote lithium-sulfur cell performance, promote the key of its industrialized development.
At present, the measure promoting lithium-sulfur cell performance is mainly carried out from following three aspects: (1) promotes the electro-chemical activity of sulfenyl active material, studying more is that sulphur and porous carbon materials form compound, see document Chem Mater, 2009,2:4724 ~ 4730 and Carbon, 2008,46:229 ~ 235; (2) suppress the dissolving of polysulfide, mainly add the method for the strong material of adsorptivity or coated active material.See the Chinese patent literature that application number is 201110086208.6 and 201110115424.9, and english literature Nature materials, 2009,8:500 ~ 506; (3) the modification protection of cathode of lithium.But still there is complicated process of preparation, adopt organic high―temperature nuclei, the problem of cyclical stability difference, also exists with a certain distance from industrialization.
In order to promote the cycle performance of lithium-sulfur cell further, seek the preparation technology being beneficial to industrialization, the present invention adopt simple process, equipment simple and the low chemical plating method of cost at elemental sulfur Surface coating conducting metal, improve the deficiency of elemental sulfur poor electric conductivity on the one hand, stop polysulfide and electrolyte contacts on the other hand, in minimizing reaction, polysulfide flies shuttle effect; Adopting twice dry method with suppressing simultaneously when preparing electrode, making active material, conductive agent and binding agent close contact, being beneficial to the diffusion of lithium ion, simultaneously the mechanical stability of intensifier electrode, promoting the performance of lithium-sulfur cell.
Summary of the invention
The object of this invention is to provide the anode pole piece of lithium-sulfur cell, by active material structure modification wherein and innovation, make it have excellent electro-chemical activity and cyclical stability.
Another object of the present invention is to provide the preparation method of above-mentioned positive pole plate of lithium-sulfur cell.
The anode pole piece of lithium-sulfur cell of the present invention is coated in collector obtains by mixing through the sulfenyl composite active material of surface modification, conductive agent and binding agent; Described sulfenyl composite active material is coated on simple substance sulphur granule by conducting metal, carry out surface modification to sulphur to obtain, described simple substance sulphur granule is 10nm ~ 10 μm, coated conducting metal thickness is 0.1 ~ 10nm, and conducting metal is 0.8 ~ 10% of the mass content of described sulfenyl composite active material.
Described conducting metal is nickel and/or copper.
The preparation method of the anode pole piece of lithium-sulfur cell of the present invention, be that binding agent and conductive agent dissolve in a solvent, add sulfenyl composite active material after magnetic agitation, stir and fully mix, by the slurry knifing that obtains on collector, form through vacuumize compacting; Described sulfenyl composite active material is by elemental sulfur coated upper conducting metal through chemical plating reduction after mechanical ball milling and activating pretreatment.
Described vacuumize is compressed to twice: vacuumize temperature is first 40 ~ 80 DEG C, and drying time is 6 ~ 12h, and tableting pressure is 1 ~ 3MPa, and baking temperature is 100 ~ 120 DEG C again, and drying time is 3 ~ 8h, and tableting pressure is 2 ~ 5Mpa, to obtain final product.
Described mechanical ball milling and activating pretreatment are after elemental sulfur mechanical ball being milled to 10nm ~ 10 μm, through cleaning, sensitization and activation processing.
Described conducting metal is copper and/or nickel.
The content of elemental sulfur is 0.01 ~ 0.1mol/L of chemical plating fluid.
Elemental sulfur described in the anode pole piece of lithium-sulfur cell of the present invention is sublimed sulfur, and conductive agent is acetylene black or superconduction carbon black, and binding agent is Kynoar, and collector is aluminium foil.
The ratio of described sulfenyl composite active material, conductive agent and binding agent is 7 ~ 8:1.5 ~ 2:0.5 ~ 1, and the concrete ratio of conductive agent and binding agent is determined according to the kind of the coated conducting metal of active material and content.
1-METHYLPYRROLIDONE solvent is adopted to mix during the mixing of described sulfenyl composite active material, conductive agent and binding agent.
Described coated conducting metal is the excellent metal of the electric conductivity such as copper or nickel.
The simple substance sulphur granule that described sulfenyl composite active material adopts is 10nm ~ 10 μm, and the conducting metal thickness of plating is 0.1 ~ 10nm, and concrete plated thickness is determined according to the granule size of selected elemental sulfur.
The content of the basis for selecting clad metal of described conductive agent is chosen.
Described binding agent is Kynoar.
In the present invention a kind of concrete preparation technology's flow process of anode pole piece of lithium-sulfur cell and condition as follows:
1, the preparation of the sulfenyl composite active material of surface modification
Elemental sulfur mechanical ball is milled to 10nm ~ 10 μm, carry out following a) ~ d) preliminary treatment of step, to ensure that clad metal is evenly coated, there is good adhesive force.
A) clean: get appropriate sulphur supersonic oscillations 10 ~ 30min in 37vol% watery hydrochloric acid, cleaning to pH with distilled water is 7, then uses ethanol purge, then with distilling washing 3 ~ 4 times;
B) sensitization: pass through the sulphur magnetic agitation process 3 ~ 10min in sensitizing solution cleaned in a), suction filtration takes out;
Composition and the sensitization technique of sensitizing solution are as follows:
The composition of sensitizing solution:
Stannous chloride (SnCl
22H
2o) 2 ~ 5g/L
Hydrochloric acid (HCl) (37vol%) 2 ~ 5mL/L
Sensitization technique:
Sensitized treatment temperature room temperature
Sensitized treatment time 3 ~ 10min
C) activate: by through sensitization plays sulphur at activating solution magnetic agitation process 1 ~ 5min, until powder precipitation after, suction filtration take out powder, with distilled water cleaning to pH be 7;
Composition and the activating process of activating solution are as follows:
The composition of activationization liquid:
Palladium bichloride (PdCl
2) 0.2 ~ 0.5g/L
Hydrochloric acid (HCl) (37vol%) 3 ~ 10mL/L
Activating process:
Activating treatment temperature room temperature
Activation processing time 1 ~ 5min
D) reduce: the powder after activation is soaked 0.5 ~ 2min, suction filtration, pending chemical plating in sodium hypophosphite solution.
Chemical plating: conducting metal is evenly coated to sulphur surface, ready powder is put into pre-configured chemical plating fluid, magnetic agitation, plating 10 ~ 120min, controls the thickness of coating layer, suction filtration with Plating times, distilled water washing 3 ~ 4 times, in vacuum drying chamber, vacuum 70 ~ 80 DEG C of drying 4 ~ 6h, the sulfenyl composite active material of obtained surface modification.
Concrete plating solution composition and technique as follows:
Chemical plating condition:
PH value 8 ~ 8.5 or 11-13
Temperature 70 ~ 90 DEG C or room temperature
Plating times 10 ~ 120min.
2, the sulfenyl composite active material of surface modification does the preparation of the electrode of active material
According to metal lining kind and the coating thickness of the sulfenyl composite active material of surface modification, get amount of conductive agent and binding agent, three is mixed, be prepared into slurry, by the thickness of electrode knifing of setting, prepare electrode through twice vacuumize and twice compressing tablet.
Concrete technology flow process and condition as follows:
The sulfenyl composite active material of surface modification is got in 7 ~ 8:1.5 in mass ratio ~ 2:0.5 ~ 1, conductive agent and binding agent, get appropriate dissolution with solvents binding agent and conductive agent, magnetic agitation 0.5 ~ 1h, then composite active material is added, stir 3 ~ 6h fully to mix to it, by the slurry knifing that obtains in aluminum foil current collector, twice drying is carried out in vacuum drying chamber, vacuumize temperature is first 40 ~ 80 DEG C, drying time is 6 ~ 12h, tableting pressure is 1 ~ 3MPa, baking temperature is 100 ~ 120 DEG C again, drying time is 3 ~ 8h, tableting pressure is 2 ~ 5MPa, obtain a kind of positive pole plate of lithium-sulfur cell.
A kind of positive pole plate of lithium-sulfur cell of the present invention, its active material is the sulfenyl composite material that Surface coating has conducting metal, and adopt the coated sulphur powder of conducting metal, tool has the following advantages: (1) improves the electric conductivity of elemental sulfur, strengthens its electro-chemical activity; (2) conducting metal is coated on sulphur surface, and the fracture that in course of reaction, coating layer is sulphur-sulfide linkage and generation provide reacting environment, slow down the dissolving of the polysulfide in reaction, suppresses " effect of shuttling back and forth " to a certain extent, promotes the cycle life of lithium-sulfur cell; (3) sulphur exists with elemental stage, and specific capacity is high; (4) granularity of sulphur powder and the thickness of coating layer controlled, can according to the kind of the granularity of sulphur powder, coating layer metal and thickness, by the conductivity of test material, the ratio of modulation active material, conductive agent and binding agent, control the addition of conductive agent and binding agent, realize the optimization of electrode, and then optimize lithium-sulfur cell performance.
The preparation method of a kind of positive pole plate of lithium-sulfur cell of the present invention, chemical plating is adopted to carry out the coated of conducting metal to elemental sulfur, structural representation is as Fig. 1, in figure, 1 is the controlled elemental sulfur of particle, 2 is the controlled conducting metal of coated thickness, tool has the following advantages: (1) is easy to the thickness of coating and the content that control conducting metal, is convenient to carry out plating to the sulphur of multiple particle size range; (2) technique is simple, with low cost, is beneficial to suitability for industrialized production; (3) coating layer is even, good with sulphur adhesion.
Simultaneously, the method of twice drying, compacting is adopted after knifing during described pole piece makes, the pole piece structure comparison diagram that after Fig. 2 gives pole piece preparation method of the present invention and traditional knifing prepared by primary drying, drawing method, pole piece 1 sulfenyl composite active material prepared by the present invention, 2 conductive agents, 3 binding agent contacts are closely, better with 4 collector adhesions, following effect can be produced: (1) strengthens the mechanical stability of pole piece, active material not easily peels off from collector, extend electrode life, promote cycle performance; (2) make sulfenyl composite active material, conductive agent contact closely with binding agent, electro-chemical activity is high, is beneficial to the diffusion of reaction intermediate ion, promotes the high rate performance of battery; (3) reduce the consumption of binding agent, increase active material quality, play the high capacity characteristics of sulphur more.
In sum, the invention has the beneficial effects as follows:
1, the present invention adopts the method for chemical plating at elemental sulfur Surface coating conducting metal, form the composite active material of surface modification, improve the electric conductivity of elemental sulfur, that reduces polysulfide in reaction to a certain extent flies shuttle effect, promotes the cycle performance of lithium-sulfur cell; Meanwhile, prepare twice dry and compacting in pole piece process, improve the mechanical stability of pole piece, make pole piece material close contact, electro-chemical activity is high.Preparation technology is simple, and cost is low, is beneficial to suitability for industrialized production.The electrode plates prepared by the inventive method and lithium metal form lithium-sulfur cell, and under room temperature 0.1C rate charge-discharge condition, first discharge specific capacity is 843.8mAh/g, and after 100 circulations, the decay of capacity is less than 8% of second time specific discharge capacity.
In the anode pole piece and preparation method thereof of 2, a kind of lithium-sulfur cell of the present invention, active material adopts the sulfenyl active composite material of surface modification, Surface coating has conducting metal, compared with not carrying out surface coated elemental sulfur and do the battery of electrode active material, first discharge specific capacity is high, and good cycle.Preparing of pole piece of the present invention adopts twice dry method with suppressing, compare with electrode prepared by drawing method with common employing primary drying, active material, the conductive agent of electrode contact with binding agent closely, be beneficial to ion diffuse, the adhesion of pole piece material and collector is good, the good cycle of battery.
Accompanying drawing explanation
Fig. 1 is surface modification active composite material schematic diagram of the present invention, and in figure, 1 is the controlled elemental sulfur of particle, and 2 is the controlled conducting metal of coated thickness.
Fig. 2 is the electrode structure comparison diagram of twice dry compacting of the present invention and the compacting of traditional primary drying, a () figure is the electrode structure schematic diagram of twice dry compacting, b () figure is the electrode structure schematic diagram of traditional primary drying compacting, in figure, 1 is the sulfenyl composite active material of surface modification, 2 is conductive agent, 3 is binding agent, and 4 is collector.
Fig. 3 is technological process of the present invention.
Fig. 4 is the particle size distribution figure after embodiment 1 elemental sulfur and coated nickel, and the particle size distribution figure that (a) is elemental sulfur, (b) is the particle size distribution figure after the coated nickel of elemental sulfur.
Fig. 5 is the SEM photo after the not coated nickel of embodiment 3 elemental sulfur and coated nickel, and (a) is the SEM photo of the not coated nickel of elemental sulfur, and (b) is the SEM photo after the coated nickel of elemental sulfur.
Fig. 6 is the first charge-discharge correlation curve of the battery of electrode assembling prepared by the sulphur active material of the coated nickel of employing that obtains of embodiment 1 and comparative example 1 and not coated nickel.
Fig. 7 is the cycle performance correlation curve of the battery of electrode assembling prepared by the sulphur active material of the coated nickel of employing that obtains of embodiment 1 and comparative example 1 and not coated nickel.
Fig. 8 is the first charge-discharge correlation curve that the sulphur active material of the coated nickel that embodiment 1 and comparative example 2 obtain adopts the battery of the electrode assembling of twice dry compacting and common primary drying compacting preparation.
Fig. 9 is the cycle performance correlation curve that the sulphur active material of the coated nickel that embodiment 1 and comparative example 2 obtain adopts the battery of the electrode assembling of twice dry compacting and common primary drying compacting preparation.
Embodiment
Below by embodiment, the present invention is further described, but does not limit the scope of the invention.
In following examples and comparative example, elemental sulfur used is sublimed sulfur, granularity is 10nm ~ 10 μm, coated conducting metal is nickel and/or copper, coated thickness is 0.1 ~ 10nm, mass percent 0.8 ~ 10wt%, sulfenyl composite active material in pole piece preparation, conductive agent and binding agent mass ratio 7 ~ 8:1.5 ~ 2:0.5 ~ 1, wherein conductive agent is acetylene carbon black, binding agent is Kynoar, solvent is 1-METHYLPYRROLIDONE, collector is aluminium foil, the granulometry of sulphur powder and coated rear composite material adopts multi-angle ultra-fine grain analyzer to measure, ionic conductivity adopts four probe method test.
The positive pole plate of lithium-sulfur cell prepared in embodiment and comparative example and lithium-sulfur cell assembled by lithium metal and method of testing is as follows:
The anode pole piece prepared is assembled button lithium-sulfur cell in the glove box of argon gas atmosphere, and pole piece prepared by the present invention makes positive pole, and lithium sheet makes negative pole, and electrolyte is LiTFSI/DOL:DEM (1:1 volume ratio, DOL:1, the 3-dioxolanes of 1mol/L; DME: glycol dimethyl ether), barrier film adopts Celgard2400, and housing adopts CR2032.Probe temperature is room temperature, and test multiplying power is 0.1C, and test voltage scope is 1.0 ~ 3.0V.The calculating of specific capacity of the present invention is the specific capacity of benchmark by the material total amount of anode pole piece.
Embodiment 1
The preparation of surface modification sulphur nickel composite active material:
[1] preliminary treatment is carried out to elemental sulfur, to ensure that clad metal is evenly coated, there is good adhesive force.
1, clean: getting 6g granularity is that the sublimed sulfur powder of about 100nm is in the beaker of 100ml, add the watery hydrochloric acid of 50ml37%, Ultrasonic Cleaning 30min at 40 DEG C, ultrasonic power is 100W, after having cleaned, cleaning to pH with distilled water is 7, then uses ethanol purge, again with distillation washing 3 times, in cleaning process, the taking-up of sulphur powder adopts suction filtration.
2, sensitization: make sulphur powder adsorption one deck reducing metal ion, will have the reducing metal ions of catalytic action for atom when subsequent activation process.
Sensitized solution forms:
Stannous chloride (SnCl
22H
2o) 4g/L
Hydrochloric acid (HCl) 4ml/L
The preparation of sensitized solution and activation process:
(1) under magnetic stirring, by the SnCl of 0.2g
22H
2o is dissolved in 0.2ml hydrochloric acid, then uses 50ml distilled water diluting, set aside for use;
(2) powder after cleaning is put into sensitizing solution, magnetic agitation 8min.
3, activate: make sulphur powder surface form the metal level that one deck has catalytic activity.
Activated solution forms:
Palladium bichloride (PdCl
2) 0.4g/L
Hydrochloric acid (HCl) 8ml/L
The preparation of activated solution and activation process:
(1) by the PdCl of 0.02g
2add in 50ml distilled water, treat to dissolve completely, add 0.4ml hydrochloric acid while stirring, stir until transparent;
(2) add activating solution by the powder of sensitization, stir 5min, leave standstill;
(3) after powder precipitation, take out sensitization and activation mixed liquor, then wash 3 ~ 5 times with distilled water.
4, reduce: after activation processing, for improving the catalytic activity of powder surface, preventing activating solution to be brought into chemical plating fluid, reduction treatment need be carried out to powder.
Reducing solution forms: 3% sodium hypophosphite solution
Recovery time: 50s
[2] chemical plating:
Chemical nickel-plating plating solution forms
Chemical plating temperature: 85 DEG C
Electroless plating time: 10min
Stirring condition: magnetic agitation
Cleaning is not needed by sulphur powder through reduction treatment directly to carry out chemical plating.
Under these conditions, obtained plated thickness is the surface modification sulphur nickel composite active material of 10nm.
Fig. 4 is the grain size analysis of the surface modification sulphur nickel composite active material that the elemental sulfur of embodiment 1 and chemical nickel plating obtain, and adopts the equivalent diameter of volume equivalence to describe the size of its particle diameter.Result shows, the average grain diameter of elemental sulfur is about 100nm, the average grain diameter of the surface modification sulphur nickel composite active material obtained after chemical nickel plating is about 110nm, found out by figure, before surface modification, the particle size distribution of elemental sulfur is at 92.3 ~ 106.8nm, wherein average grain diameter is that the elemental sulfur of 103.5nm accounts for 56.2%, other two kinds of particle diameters account for 41.9% and 1.9% respectively; After surface modification, the particle size distribution of sulphur nickel composite active material is at 103.1 ~ 117.2nm, and wherein particle diameter is that the composite material of 117.2nm accounts for 83.9%, other two kinds of particle diameters account for 11.2% and 4.9% respectively
The preparation of surface modification sulphur nickel composite active material electrode: according to active material: conductive agent: the ratio of binding agent is that 70:20:10 prepares anode pole piece, binder solution is prepared by the 1-METHYLPYRROLIDONE solution that 0.6g Kynoar is dissolved in 2ml, 1.2g conductive agent acetylene black is added under strong magnetic agitation, obtain dispersion soln, then the above-mentioned nucleocapsid structure sulphur nickel composite active material through surface modification of 4.2g is added, magnetic agitation more than dispersion soln 24h, obtained anode sizing agent.Regulate scraper to scrape film thickness, the slurry mixed is coated in aluminum foil current collector, vacuumize 8h at 80 DEG C, at the tableting under pressure of 3MPa, then vacuumize 5h at 100 DEG C, at the tableting under pressure of 5MPa, obtained sulfur electrode pole piece.
Embodiment 2
The preparation of surface modification sulphur copper composite active material: except reduction and chemical plating employing solution composition below and technique, prepare positive electrode active materials and electrode by the step identical with embodiment 1.
Reducing solution forms: 10% formaldehyde
Recovery time: 30s
Chemical plating
Electroless copper plating solution forms
Stirring condition: magnetic agitation
Cleaning is not needed by sulphur powder through reduction treatment directly to carry out chemical plating.
Under these conditions, obtained plated thickness is the surface modification sulphur copper composite active material of 10nm, and is active material with this material, and the method adopting embodiment 1 to make electrode has prepared electrode.
Embodiment 3
Except sulphur powder particles is 10 μm, the technique identical with embodiment 1 is adopted to prepare surperficial modified sulphur nickel composite active material and electrode.
Fig. 5 is the SEM photo in embodiment 3 after the not coated nickel of elemental sulfur and coated nickel, and as can be seen from the figure, before not coated nickel, elemental sulfur pattern is mellow and full, presents cellular, and thin film appears in the elemental sulfur surface after coated, and porous disappears.Infer after coated, nickel enters in the hole of elemental sulfur, is coated on the surface of simple substance sulphur granule simultaneously, strengthens the conductivity of elemental sulfur, promotes the performance of lithium-sulfur cell.
Comparative example 1
According to sulphur active material: conductive agent: the ratio of binding agent is that 70:20:10 prepares anode pole piece, binder solution is prepared by the 1-METHYLPYRROLIDONE solution that 0.6g Kynoar is dissolved in 2ml, 1.2g conductive agent acetylene black is added under strong magnetic agitation, obtain dispersion soln, then the sulphur powder that 4.2g granularity is about 100nm is added, magnetic agitation more than dispersion soln 24h, obtained anode sizing agent.Scraper is regulated to scrape film thickness, the slurry mixed is coated in aluminum foil current collector, vacuumize 8h at 80 DEG C, at the tableting under pressure of 3MPa, then vacuumize 5h at 100 DEG C, at the tableting under pressure of 5MPa, the sulfur electrode pole piece of not coated nickel prepared by obtained employing twice drying and drawing method.
Comparative example 2
Anode sizing agent is obtained by the method identical with embodiment 1, film thickness scraped by adjustment scraper, the slurry mixed is coated in aluminum foil current collector, vacuumize 8h at 80 DEG C, after the tableting under pressure of 3MPa, the pole piece that the sulphur active material obtaining coated nickel adopts common primary drying drawing method to prepare.
By embodiment 1,2,3 and the obtained electrode plates punching of comparative example 1,2, after weighing, put into argon gas atmosphere glove box, assembling button lithium-sulfur cell take lithium metal as negative pole, electrolyte is LiTFSI/DOL:DEM (1:1 volume ratio, DOL:1, the 3-dioxolanes of 1mol/L; DME: glycol dimethyl ether), barrier film adopts Celgard2400, and housing adopts CR2032.By the battery standing 24h assembled, at room temperature, test it with the multiplying power of 0.1C, test voltage scope is relative to Li/Li
+be 1.0 ~ 3.0V.With pole piece material total amount for benchmark specific capacity, test result is as shown in table 1.
Table 1
As can be seen from Table 1, the battery of the electrode assembling that the first discharge specific capacity of the battery that electrode assembling provided by the invention is good is prepared higher than the active material not carrying out surface modification in comparative example 1, and the specific discharge capacity after 100 circulations is more than 90% of second time specific discharge capacity; Twice dry, electrode first discharge specific capacity prepared by drawing method and cycle performance is all better than primary drying, prepared by drawing method electrode after the knifing that the present invention adopts.
Fig. 6 and Fig. 7 is respectively first discharge specific capacity and the cycle performance comparison diagram of embodiment 1 and comparative example 1, result shows, surface modification sulphur nickel composite active material provided by the invention does active material, twice dry, drawing method prepares the electrode that pole piece method makes, after being assembled into battery, first discharge specific capacity is 843.8mAh/g, after 50 circulations, capability retention is after second time 96.2%, 100 times of specific discharge capacity circulations be still 92.4%.
Fig. 8 and Fig. 9 is respectively first discharge specific capacity and the cycle performance comparison diagram of embodiment 1 and comparative example 2, result shows, after adopting same active material to be assembled into battery, the electrode that after comparative example 2 knifing prepared by primary drying, drawing method, the battery first discharge specific capacity provided is 639.7mAh/g, after 50 circulations, capability retention is 88.3% of second time specific discharge capacity, lower than capability retention 96.2% after twice dry, first discharge specific capacity 843.8mAh/g and 50 circulation that drawing method prepares electrode after knifing provided by the invention.
Claims (5)
1. the preparation method of the anode pole piece of a lithium-sulfur cell, it is characterized in that: binding agent and conductive agent dissolve in a solvent, add sulfenyl composite active material after magnetic agitation, stir and fully mix, by the slurry knifing that obtains on collector, form through vacuumize compacting; Described sulfenyl composite active material be by elemental sulfur after mechanical ball milling and activating pretreatment through chemical plating reduce coated upper conducting metal;
Described mechanical ball milling and activating pretreatment are after elemental sulfur mechanical ball being milled to 10nm ~ 10 μm, through cleaning, sensitization and activation processing;
In activation process, sensitizing solution is composed as follows:
The composition of sensitizing solution:
In activation process, activating solution is composed as follows:
The composition of activating solution:
The composition of the chemical plating fluid of chemical plating:
Chemical plating condition:
PH value 8 ~ 8.5 or 11-13
Temperature 70 ~ 90 DEG C or room temperature
Plating times 10 ~ 120min.
2. preparation method according to claim 1, it is characterized in that, described vacuumize is compressed to twice: vacuumize temperature is first 40 ~ 80 DEG C, drying time is 6 ~ 12h, tableting pressure is 1 ~ 3MPa, and baking temperature is 100 ~ 120 DEG C again, and drying time is 3 ~ 8h, tableting pressure is 2 ~ 5Mpa, to obtain final product.
3. preparation method according to claim 1, is characterized in that, described conducting metal is copper and/or nickel.
4. preparation method according to claim 1, is characterized in that, the content of elemental sulfur is 0.01 ~ 0.1mol/L of chemical plating fluid.
5. preparation method according to claim 1, is characterized in that conductive agent is acetylene black and superconduction carbon black; Binding agent is Kynoar.
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| CN108123167B (en) * | 2016-11-28 | 2020-04-17 | 中国科学院大连化学物理研究所 | Electrode for lithium-sulfur battery, preparation method of electrode and lithium-sulfur battery structure comprising electrode |
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| CN108987706A (en) * | 2018-07-18 | 2018-12-11 | 东莞理工学院 | A kind of lithium-sulfur cell long-life composite sulfur active material and preparation method thereof |
| CN109686978B (en) * | 2018-12-03 | 2022-11-22 | 河南师范大学 | Alkaline secondary battery iron electrode additive, preparation method, iron-based negative plate using additive and application |
| CN109755499B (en) * | 2018-12-03 | 2022-11-22 | 河南师范大学 | Iron-nickel secondary battery negative electrode additive, preparation method, iron-based negative plate using additive and application |
| CN110911682B (en) * | 2019-11-06 | 2021-03-30 | 华南理工大学 | Electrode of lithium-sulfur battery and preparation method and application thereof |
| TWI762238B (en) * | 2021-03-12 | 2022-04-21 | 國立成功大學 | A method for the fabrication of an electroless-metal-plated sulfur nanocomposite, an electroless-metal-plated sulfur cathode which is made from the nanocomposite, and a battery that uses the cathode |
| CN114420906A (en) * | 2022-01-07 | 2022-04-29 | 上海交通大学 | Chemical nickel plating based electrode material with core-shell structure, preparation method thereof and lithium-sulfur battery |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1427491A (en) * | 2001-12-18 | 2003-07-02 | 三星Sdi株式会社 | Cathode and its preparing process, and lithium-sulfur cell using this cathode |
| CN1485941A (en) * | 2002-09-23 | 2004-03-31 | ����Sdi��ʽ���� | Positive active material of a lithium-sulfur battery and method of fabricating same |
| CN102208645A (en) * | 2011-05-05 | 2011-10-05 | 中国东方电气集团有限公司 | Lithium sulfur battery anode composite material, anode and lithium sulfur battery |
| CN102723470A (en) * | 2012-06-11 | 2012-10-10 | 中国科学院物理研究所 | Lithium-sulfur battery anode material comprising porous metal and preparation method thereof |
-
2012
- 2012-12-07 CN CN201210524803.8A patent/CN103035879B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1427491A (en) * | 2001-12-18 | 2003-07-02 | 三星Sdi株式会社 | Cathode and its preparing process, and lithium-sulfur cell using this cathode |
| CN1485941A (en) * | 2002-09-23 | 2004-03-31 | ����Sdi��ʽ���� | Positive active material of a lithium-sulfur battery and method of fabricating same |
| CN102208645A (en) * | 2011-05-05 | 2011-10-05 | 中国东方电气集团有限公司 | Lithium sulfur battery anode composite material, anode and lithium sulfur battery |
| CN102723470A (en) * | 2012-06-11 | 2012-10-10 | 中国科学院物理研究所 | Lithium-sulfur battery anode material comprising porous metal and preparation method thereof |
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